CN105061486A - Preparation method of acidic cross-linking agent - Google Patents
Preparation method of acidic cross-linking agent Download PDFInfo
- Publication number
- CN105061486A CN105061486A CN201510476763.8A CN201510476763A CN105061486A CN 105061486 A CN105061486 A CN 105061486A CN 201510476763 A CN201510476763 A CN 201510476763A CN 105061486 A CN105061486 A CN 105061486A
- Authority
- CN
- China
- Prior art keywords
- product
- linking agent
- reaction
- acidic cross
- propyl group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
The invention relates to a preparation method of an acidic cross-linking agent, which belongs to the technical field of organic chemistry. According to the invention, propyl trimethoxy silane and glacial acetic acid are taken as raw materials; hexamethylphosphoric triamide is taken as a catalyst, the acidic cross-linking agent product can be synthesized through a group exchange reaction, in the reaction process, by-product methanol is steamed out of the reaction system, and chemical reaction moves to the direction of generation of the acidic cross-linking agent. The method is a substitution method of the acidic cross-linking agent, the method technology is simple and is suitable for industrial scale production, compared with the current preparation method of the acidic cross-linking agent, the by-product with strong corrosivity and difficult treatment can not be generated; no side reaction for influencing the product quality of the acidic cross-linking agent is generated; especially the product content. In addition, the raw materials do not contain chlorine, so that the prepared acidic cross-linking agent product has low free chlorine.
Description
Technical field
The present invention relates to a kind of preparation method of acidic crosslinking agent; Belong to technical field of organic chemistry.
Background technology
Acidic crosslinking agent is the one in silane coupling agent, and its acyloxy is compared with other groups as methoxyl group, oxyethyl group are more active, and decomposition rate is fast, water-disintegrable better, be conducive to improving operating efficiency, the acetic acid that hydrolysis is separated out is more weak, less to reaction system harm.Therefore better to adhesive effects such as enhancing aluminium alloy, nylon, glass and potteries, it is mainly used as the linking agent of RTV-1 silicone rubber sealant; The surface treatment agent of glass fibre; Coupling agent and silated reagent.
The raw material propyl trimethoxy silicane of synthetic acidic linking agent is prepared from by the by product of γ-r-chloropropyl trimethoxyl silane, and γ-r-chloropropyl trimethoxyl silane is the important raw and processed materials of synthesis a series of γ-functional group's silane coupling agent.In current industrial production, be often attended by the by product accounting for quality product 20% and generate.Along with the expansion of its Application Areas, demand also increases rapidly, thus causes a large amount of appearance of by product.The major ingredient of this by product is tetramethoxy-silicane and n-propyl trimethoxy silicane, tetramethoxy-silicane may be used for selling, and propyl trimethoxy silicane market is little, can not sell completely, thus with its synthetic acidic linking agent product, can realize turning waste into wealth, environmental protection and economy, is conducive to the comprehensive utilization of organosilicon resource.At present, the preparation method of acidic crosslinking agent comparative maturity has the following two kinds:
First method is using carboxylic acid as acyl-oxygen agent, and reaction equation is as follows:
CH3CH2CH2SiCl3+3CH3COOH
CH3CH2CH2Si(OOCCH3)3+3HCl
The major advantage of the method is that raw material is easily purchased, and cheaply, but reaction is more difficult, produce corrosive byproduct hydrogen chloride, there is side reaction simultaneously, affect product content, and product free chlorine is wayward.
Second method is using diacetyl oxide as acyl-oxygen agent, and reaction equation is as follows:
CH3CH2CH2SiCl3+3[CH3CO]2O
CH3CH2CH2Si(OOCCH3)3+3CH3COl
The major advantage of the method is for reacting simple, and without side reaction, but raw material is not easily purchased, and somewhat expensive, produces not tractable corrosive byproducts Acetyl Chloride 98Min., and product free chlorine is wayward simultaneously.
For many deficiencies of current acidic crosslinking agent preparation technology, be necessary to study a kind of acidic crosslinking agent preparation method, the deficiency of existing preparation technology can be overcome, industrialization scale operation can be applicable to again.
Summary of the invention
The object of the invention is to: a kind of deficiency that can overcome existing preparation technology is provided, the preparation method of the acidic crosslinking agent of industrialization scale operation can be applicable to again.
Technical scheme of the present invention is:
A preparation method for acidic crosslinking agent, is characterized in that: it comprises the following steps:
1) in the 2000ml there-necked flask being connected with magnetic agitation, still head, condenser west tube, the adapter of sub-thread vacuum tail, 1000ml single port receiving bottle, add propyl trimethoxy silicane, glacial acetic acid and HMPA, 50 ~ 75 DEG C are warming up under the stirring velocity of 80 ~ 100 revs/min, keep this thermotonus 3 ~ 6h, reaction is omnidistance keeps normal pressure, has a small amount of methyl alcohol to collect in receiving flask in reaction process;
2) crude product step 1 is obtained by reacting, air distillation is carried out under the condition of pressure 101KPa, temperature 65 ~ 120 DEG C, the air distillation time is 1 ~ 2h, collect the methyl alcohol of transesterification reaction by-product, then under the condition of pressure 0 ~-0.098Mpa, temperature 120 ~ 140 DEG C, again underpressure distillation is carried out, by low distillation of boiling is clean on a small quantity, obtain the thick product of propyl group triacetoxysilane;
3) the thick product of propyl group triacetoxysilane step 2 obtained is cooled to 70-80 DEG C, then gac is added, stir 2h with the speed of 80 ~ 100 revs/min, after be cooled to less than 40 DEG C and filter, filter the colourless transparent liquid obtained and be propyl group triacetoxysilane product.
Reaction equation of the present invention is as follows:
CH3CH2CH2Si(OCH3)3+3CH3COOH
CH3CH2CH2Si(OOCCH3)3+3CH3OH
Advantage of the present invention is:
The present invention with propyl trimethoxy silicane and glacial acetic acid for raw material; HMPA is catalyzer, by base exchange Reactive Synthesis acidic crosslinking agent product, catalyst charge is 0.002% ~ 0.01% of propyl trimethoxy silicane charging capacity, early stage is still temperature 50 DEG C ~ 75 DEG C, 3 ~ 6h is reacted under condition of normal pressure, then limit reaction, the methyl alcohol of limit air distillation transesterify by-product, distillation time is 1 ~ 2h, still temperature is 65 ~ 120 DEG C, after air distillation, continues underpressure distillation again under the condition of pressure 0 ~-0.098Mpa, temperature 120 ~ 140 DEG C, by low distillation of boiling is clean on a small quantity, obtain the thick product of propyl group triacetoxysilane; Thick product obtains content >=96.0% after decolouring, filtration, free chlorine≤10ppm, the propyl group triacetoxysilane product of mass yield (calculating with propyl trimethoxy silicane charging capacity) >=140%: the many deficiencies that instant invention overcomes current acidic crosslinking agent preparation technology, are applicable to industrialization scale operation.
Embodiment
Embodiment 1
In the 2000ml there-necked flask being connected with magnetic agitation, still head, condenser west tube (being connected with cooling tap water), the adapter of sub-thread vacuum tail, 1000ml single port receiving bottle, add 492g propyl trimethoxy silicane, 540g glacial acetic acid and 0.03g HMPA, 75 DEG C are warming up under the stirring velocity of 100 revs/min, keep this thermotonus 6h, reaction is omnidistance keeps normal pressure, has a small amount of methyl alcohol to collect in receiving flask in reaction process; The crude product will be obtained by reacting after completion of the reaction, air distillation is carried out under the condition of pressure 101KPa, temperature 75 DEG C, the air distillation time is 2h, collect the methyl alcohol 256g of transesterification reaction by-product, then under the condition of pressure 0 ~-0.098Mpa, temperature 130 DEG C, again underpressure distillation is carried out, collect the remaining low 50g that boils, obtain the thick product of propyl group triacetoxysilane; The thick product of propyl group triacetoxysilane obtained is cooled to 80 DEG C, then add 5g gac, stir 2h with the speed of 100 revs/min, after be cooled to less than 40 DEG C and filter, filter the propyl group triacetoxysilane product 726g obtaining colourless transparent liquid, product content: 96.5%; Free chlorine: 5ppm; Mass yield: 147.5%.
Embodiment 2
In the 2000ml there-necked flask being connected with magnetic agitation, still head, condenser west tube (being connected with cooling tap water), the adapter of sub-thread vacuum tail, 1000ml single port receiving bottle, add 492g propyl trimethoxy silicane, 540g glacial acetic acid, 0.03g HMPA, 70 DEG C are warming up under the stirring velocity of 90 revs/min, keep this thermotonus 5h, reaction is omnidistance keeps normal pressure, has a small amount of methyl alcohol to collect in receiving flask in reaction process; The crude product will be obtained by reacting after completion of the reaction, air distillation is carried out under the condition of pressure 101KPa, temperature 120 DEG C, the air distillation time is 1.5h, collect the methyl alcohol 250g of transesterification reaction by-product, then under the condition of pressure 0 ~-0.098Mpa, temperature 140 DEG C, again underpressure distillation is carried out, collect the remaining low 70g that boils, obtain the thick product of propyl group triacetoxysilane; The thick product of propyl group triacetoxysilane obtained is cooled to 75 DEG C, then add 5g gac, stir 2h with the speed of 90 revs/min, after be cooled to less than 40 DEG C and filter, filter the propyl group triacetoxysilane product 712g obtaining colourless transparent liquid, product content: 96.8%; Free chlorine: 7ppm; Mass yield: 144.7%.
Embodiment 3
In the 2000ml there-necked flask being connected with magnetic agitation, still head, condenser west tube (being connected with cooling tap water), the adapter of sub-thread vacuum tail, 1000ml single port receiving bottle, add 492g propyl trimethoxy silicane, 540g glacial acetic acid, 0.05g HMPA, 60 DEG C are warming up under the stirring velocity of 100 revs/min, keep this thermotonus 5h, reaction is omnidistance keeps normal pressure, has a small amount of methyl alcohol to collect in receiving flask in reaction process; The crude product will be obtained by reacting after completion of the reaction, air distillation is carried out under the condition of pressure 101KPa, temperature 90 DEG C, the air distillation time is 1.5h, collect the methyl alcohol 248g of transesterification reaction by-product, then under the condition of pressure 0 ~-0.098Mpa, temperature 130 DEG C, again underpressure distillation is carried out, collect the remaining low 63g that boils, obtain the thick product of propyl group triacetoxysilane; The thick product of propyl group triacetoxysilane obtained is cooled to 80 DEG C, then add 5g gac, stir 2h with the speed of 100 revs/min, after be cooled to less than 40 DEG C and filter, filter the propyl group triacetoxysilane product 721g obtaining colourless transparent liquid, product content: 96.3%; Free chlorine: 3ppm; Mass yield: 146.5%.
Embodiment 4
In the 2000ml there-necked flask being connected with magnetic agitation, still head, condenser west tube (being connected with cooling tap water), the adapter of sub-thread vacuum tail, 1000ml single port receiving bottle, add 492g propyl trimethoxy silicane, 540g glacial acetic acid, 0.05g HMPA, 65 DEG C are warming up under the stirring velocity of 100 revs/min, keep this thermotonus 3h, reaction is omnidistance keeps normal pressure, has a small amount of methyl alcohol to collect in receiving flask in reaction process; The crude product will be obtained by reacting after completion of the reaction, air distillation is carried out under the condition of pressure 101KPa, temperature 115 DEG C, the air distillation time is 1h, collect the methyl alcohol 222g of transesterification reaction by-product, then under the condition of pressure 0 ~-0.098Mpa, temperature 120 DEG C, again underpressure distillation is carried out, collect the remaining low 103g that boils, obtain the thick product of propyl group triacetoxysilane; The thick product of propyl group triacetoxysilane obtained is cooled to 80 DEG C, then add 5g gac, stir 2h with the speed of 100 revs/min, after be cooled to less than 40 DEG C and filter, filter the propyl group triacetoxysilane product 707g obtaining colourless transparent liquid, product content: 96.3%; Free chlorine: 3ppm; Mass yield: 143.7%.
Claims (1)
1. a preparation method for acidic crosslinking agent, is characterized in that: it comprises the following steps:
1), in the 2000ml there-necked flask being connected with magnetic agitation, still head, condenser west tube, the adapter of sub-thread vacuum tail, 1000ml single port receiving bottle, add propyl trimethoxy silicane, glacial acetic acid and HMPA, 50 ~ 75 DEG C are warming up under the stirring velocity of 80 ~ 100 revs/min, keep this thermotonus 3 ~ 6h, reaction is omnidistance keeps normal pressure, has a small amount of methyl alcohol to collect in receiving flask in reaction process;
2) crude product, step 1 is obtained by reacting, air distillation is carried out under the condition of pressure 101KPa, temperature 65 ~ 120 DEG C, the air distillation time is 1 ~ 2h, collect the methyl alcohol of transesterification reaction by-product, then under the condition of pressure 0 ~-0.098Mpa, temperature 120 ~ 140 DEG C, again underpressure distillation is carried out, by low distillation of boiling is clean on a small quantity, obtain the thick product of propyl group triacetoxysilane;
3) the thick product of propyl group triacetoxysilane, step 2 obtained is cooled to 70-80 DEG C, then gac is added, stir 2h with the speed of 80 ~ 100 revs/min, after be cooled to less than 40 DEG C and filter, filter the colourless transparent liquid obtained and be propyl group triacetoxysilane product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510476763.8A CN105061486B (en) | 2015-08-07 | 2015-08-07 | A kind of preparation method of acidic crosslinking agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510476763.8A CN105061486B (en) | 2015-08-07 | 2015-08-07 | A kind of preparation method of acidic crosslinking agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105061486A true CN105061486A (en) | 2015-11-18 |
| CN105061486B CN105061486B (en) | 2017-12-15 |
Family
ID=54491046
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510476763.8A Active CN105061486B (en) | 2015-08-07 | 2015-08-07 | A kind of preparation method of acidic crosslinking agent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105061486B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108358963A (en) * | 2018-03-14 | 2018-08-03 | 广州雷斯曼新材料科技有限公司 | A kind of acidic crosslinking agent and preparation method thereof applied to silicone sealant |
| CN114315890A (en) * | 2022-01-05 | 2022-04-12 | 湖北江瀚新材料股份有限公司 | Preparation method of methacryloxypropyl triacetoxysilane |
| CN114430757A (en) * | 2019-09-27 | 2022-05-03 | 赢创运营有限公司 | Silicone (meth) acrylates, method for the production thereof and use thereof in curable compositions |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5187291A (en) * | 1991-04-18 | 1993-02-16 | Huls Aktiengesellschaft | Process for the simultaneous and continuous preparation of acyloxysilanes and carboxylic acid chlorides |
| CN104558012A (en) * | 2015-01-27 | 2015-04-29 | 荆州市江汉精细化工有限公司 | Preparation method of propyltriacetoxysilane |
-
2015
- 2015-08-07 CN CN201510476763.8A patent/CN105061486B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5187291A (en) * | 1991-04-18 | 1993-02-16 | Huls Aktiengesellschaft | Process for the simultaneous and continuous preparation of acyloxysilanes and carboxylic acid chlorides |
| CN104558012A (en) * | 2015-01-27 | 2015-04-29 | 荆州市江汉精细化工有限公司 | Preparation method of propyltriacetoxysilane |
Non-Patent Citations (1)
| Title |
|---|
| 李飞: "乙基三乙酰氧基硅烷与六甲基二硅烷的合成研究", 《万方学位论文全文数据库》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108358963A (en) * | 2018-03-14 | 2018-08-03 | 广州雷斯曼新材料科技有限公司 | A kind of acidic crosslinking agent and preparation method thereof applied to silicone sealant |
| CN114430757A (en) * | 2019-09-27 | 2022-05-03 | 赢创运营有限公司 | Silicone (meth) acrylates, method for the production thereof and use thereof in curable compositions |
| CN114315890A (en) * | 2022-01-05 | 2022-04-12 | 湖北江瀚新材料股份有限公司 | Preparation method of methacryloxypropyl triacetoxysilane |
| CN114315890B (en) * | 2022-01-05 | 2023-11-17 | 湖北江瀚新材料股份有限公司 | Preparation method of methacryloxypropyl triacetoxy silane |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105061486B (en) | 2017-12-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104177250A (en) | Process for producing glycollic acid from methyl glycolate | |
| CN105131028B (en) | A kind of preparation method of MTES | |
| CN105504287A (en) | Preparation methods and application of silane oligomer composition | |
| CN104592030A (en) | Method for synthesizing phthalate compounds | |
| CN105061486A (en) | Preparation method of acidic cross-linking agent | |
| CN105646570A (en) | Novel organic titanate butanediol titanium, and synthesis method and application thereof | |
| CN102250449A (en) | Process for synthesizing saturated polyester resin by using recycled terephthalic acid | |
| CN114315888A (en) | Environment-friendly method for synthesizing organic compound based on Grignard method | |
| CN111393331B (en) | Preparation method of glycocyamine | |
| CN105418668A (en) | Preparation method for 3-acryloyloxy propyl trimethoxysilane | |
| CN106748630A (en) | A kind of synthetic method of antalgesic intermediate Bromomethylcyclobutane | |
| CN101709055A (en) | Method for synthesizing ionic liquid | |
| CN101967081B (en) | Process for recovering water-containing methanol solution produced in production of antioxygen 1010 | |
| CN110452089A (en) | The synthetic method of p-chloromethyl styrene | |
| CN104277027A (en) | Preparation method of (R)-propylene carbonate | |
| CN104230662A (en) | Preparation method of high-purity 5N aluminum isopropoxide | |
| CN101182329B (en) | Method for hydrolyzing methyl phenyl siloxane | |
| CN104592283A (en) | Synthetic method of silane coupling agent Si-69 | |
| CN104803858B (en) | A method of preparing 4-butyl ammonium fluoride trihydrate | |
| CN110615421A (en) | Preparation method of silicon dioxide material for fluorine transfer | |
| CN102442958B (en) | Preparation method of isomer-removed tebuconazole | |
| CN102766051A (en) | Method for preparing benzyl benzoate by oxidizing dibenzyl ether | |
| CN114835557B (en) | Method for co-production of TMDD by using MIBK as solvent | |
| CN114805248B (en) | Comprehensive utilization method of industrial low-concentration acetic acid | |
| CN106279248B (en) | A method of preparing neutral organosilicon hydrolyzation object |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP03 | Change of name, title or address | ||
| CP03 | Change of name, title or address |
Address after: Luochang Town, Shashi District, Jingzhou City, Hubei Province Patentee after: Hubei Jianghan New Material Co.,Ltd. Address before: 434000 No.2 Road, Shashi District Economic and Technological Development Zone, Jingzhou City, Hubei Province Patentee before: JINGZHOU JIANGHAN FINE CHEMICAL Co.,Ltd. |